JP6596412B2 - Thermosetting resin composition having diene / dienophile pair and repairability - Google Patents

Description

  Semiconductor devices (collectively “subcomponents”), such as chip size or chip scale package (“CSP”), ball grid array (“BGA”), land grid array (“LGA”) and the like, or semiconductor chips Is provided for providing a thermosetting resin composition useful for mounting on a circuit board. The reaction product of the composition can be repaired in a controlled manner under appropriate conditions.

  Due to their popularity, portable display devices have increased dramatically in recent years. Accordingly, attempts are being made to increase manufacturing through-out to meet growing demand. A particularly troublesome area for manufacturers is the handling and handling of defective subcomponents. For example, during the manufacture of circuit board subassemblies, a number of semiconductor devices are electrically connected to the substrate. The substrate is then tested to evaluate function. The substrate may be defective. In such cases, it is desirable to identify the semiconductor device that caused the failure, remove it from the substrate, and reuse the substrate with the remaining functional semiconductor devices.

  Typically, subcomponents are connected to electrical conductors (or metallization) on the circuit board using solder connections. However, when the resulting subassembly is exposed to thermal cycling, vibration, strain, or falls, the reliability of the solder connection between the circuit board and the subcomponent is often questionable. After the subcomponent is mounted on the circuit board, the space between the subcomponent and the circuit board is usually with sealing resin (commonly called underfill sealant) to relieve stress caused by thermal cycling This improves thermal shock characteristics and improves the reliability of the assembly structure.

  However, since a thermosetting resin composition that forms a crosslinked network when cured is typically used as an underfill encapsulant, if the subcomponent is defective after being mounted on a circuit board, It is difficult to replace subcomponents without destroying or scraping the entire subassembly so formed.

  Even under the latest technology, the underfill encapsulant flows quickly by capillary action in the underfill space between the subcomponent or semiconductor chip and the circuit board; cures quickly under low temperature conditions; good Easy to use with underfill encapsulant under conditions that provide high productivity and thermal shock resistance and do not compromise the remaining subcomponents or semiconductor chips remaining on the substrate or the intact state of the substrate itself And can be easily separated from the defective subcomponent or semiconductor chip; if the defective subcomponent or semiconductor chip once assembled on the circuit board is defective, the underfill encapsulant is repaired It is desirable to be possible.

  A thermosetting resin composition useful as an underfill sealing material is provided. The composition allows the subcomponent or semiconductor chip to be firmly connected to the circuit board with short heat curing and good productivity, which has excellent thermal shock properties (or thermal cycling properties) When the subcomponent or the semiconductor chip or the connection is defective, the subcomponent or the semiconductor chip can be easily removed from the circuit board.

  The reaction products of these compositions can be repaired in a controlled manner through softening and loss of adhesion, such as by exposure to higher temperature conditions than those used to cure the compositions. .

  More specifically, the composition of the present invention comprises a curable resin component and a curing agent, and in one embodiment a diene / dienophile pair functionalized with at least two carboxylic acid groups, and in another embodiment, a curable composition. A diene / dienophile pair is provided that is functionalized with at least two groups that are reactive with the resin component, at least one of which is not a carboxylic acid group.

  In each of these embodiments, the reaction product of the inventive composition is degradable in a controlled manner upon exposure to higher temperature conditions than those used to cure the composition.

  Although the composition of the present invention can be cured at a relatively low temperature in a short time, the cured reaction product has excellent thermal shock characteristics and can be easily divided by application of force under heating conditions. can do. That is, the subcomponent or semiconductor chip attached to the circuit board by the cured reaction product of the thermosetting resin composition of the present invention can be easily removed by heating the reaction product.

  Through the use of the composition of the present invention, the subcomponent or semiconductor chip can be firmly connected to the circuit board with short heat curing and good productivity, and the resulting subassembly has excellent heat Indicates impact characteristics (or thermal cycle characteristics). In addition, in the case of failure, the subcomponent or semiconductor chip can be easily removed. As a result, the circuit board can be reused, so that the yield of the production process is improved and the production cost is reduced.

  The benefits and advantages of the present invention will become more readily apparent after reading the Detailed Description of the Invention with reference to the drawings.

FIG. 1 is a cross-sectional view showing an example of a semiconductor device in which the thermosetting resin composition of the present invention is used. FIG. 2 is a sectional view showing an example of a semiconductor flip chip assembly in which the thermosetting resin composition of the present invention is used. FIG. 3 is a flow diagram of a procedure useful for repairing a cured thermosetting resin composition according to the present invention to remove a semiconductor device from an attached circuit board. FIG. 4 is a diagram showing a storage elastic modulus trace with respect to temperature for samples A to D. FIG. FIG. 5 is a diagram showing a storage elastic modulus trace with respect to temperature for samples E and F. FIG. FIG. 6 is a diagram showing a trace of storage elastic modulus with respect to temperature for sample L. FIG. FIG. 7 is a diagram showing a trace of storage elastic modulus with respect to temperature for sample M. FIG. FIG. 8 is a diagram showing a storage elastic modulus trace with respect to temperature for sample N. FIG. FIG. 9 is a diagram showing a storage elastic modulus trace with respect to temperature for HYSOL UF3808. FIG. 10 is a diagram showing a tan delta trace against temperature for each of the samples shown in Table 7. FIG.

  As described above, the composition of the present invention comprises a curable resin component and a curing agent, and in one embodiment a diene / dienophile pair functionalized with at least two carboxylic acid groups, and in another embodiment, a curable resin component. Provides a diene / dienophile pair functionalized with at least two groups that are reactive with at least one of which is not a carboxylic acid group.

  The diene / dienophile pairs are dicyclopentadiene, cyclopentadiene-maleimide, cyclopentadiene-maleate, cyclopentadiene-fumarate, cyclopentadiene- (meth) acrylate, cyclopentadiene-crotonate, cyclopentadiene-cinnamate, cyclopentadiene- (meth) acrylamide Or furan-maleimide may be selected.

  The diene of the diene / dienophile pair may be selected from acyclic 1,3-diene, cyclopentadiene, cyclohexadiene, furan, fulvene, pyrrole, naphthalene and anthracene.

  The diene / dienophile dienophile is cyclopentadiene, maleimide, isomaleimide, citraconimide, itaconimide, maleate, crotonate, cinnamate, fumarate, (meth) acrylate, cyanoacrylate, benzoquinone, benzoquinone oxime, benzoquinoneimine, naphthaquinone, alkylidenemalonate , (Meth) acrylamide, and alkynes containing electron withdrawing groups. In particular, cyclopentadiene may be considered both a diene and a dienophile.

  The diene / dienophile pair is a compound within structure I:

（式中、ＸはＣＨ_２、Ｃ＝ＣＨ_２、Ｃ＝Ｏ、Ｃ＝ＳまたはＣ＝ＮＲであり、このＲはＨ、アルキル、アリールまたはアラルキルであり；ＹはＯ、ＳまたはＮＲであり、このＲはＨ、アルキル、アリールまたはアラルキルであり；Ａはアルキレンであり；ＺはＨ、（メタ）アクリロイル、グリシジル、または重合性官能基、例えばエポキシ（グリシジル以外）、エピスルフィド、（メタ）アクリレート（（メタ）アクリロイル以外）、（メタ）アクリルアミド、マレイミド、マレエート、フマレート、シンナメート、クロトネート、オキセタン、チオキセタン、アリル、スチレン類、オキサジン（例えばベンズオキサジン）、オキサゾリン、Ｎ−ビニルアミドおよびビニルエーテルなどを含む基であり；ｎは０または１であり；ｍは２〜４である）に包含されてもよい。

Wherein X is CH ₂ , C═CH ₂ , C═O, C═S or C═NR, where R is H, alkyl, aryl or aralkyl; Y is O, S or NR Where R is H, alkyl, aryl or aralkyl; A is alkylene; Z is H, (meth) acryloyl, glycidyl, or a polymerizable functional group such as epoxy (other than glycidyl), episulfide, (meth) acrylate Groups containing (other than (meth) acryloyl), (meth) acrylamide, maleimide, maleate, fumarate, cinnamate, crotonate, oxetane, thioxetane, allyl, styrenes, oxazines (eg benzoxazine), oxazoline, N-vinylamide and vinyl ether N is 0 or 1; m is 2-4 May be included).

  The diene / dienophile pair is a compound within structure II:

（式中、Ｘ_１およびＸ_２は、同じでありまたは異なり、それぞれ独立してＣＨ_２、Ｃ＝ＣＨ_２、Ｃ＝Ｏ、Ｃ＝ＳまたはＣ＝ＮＲから選択され、このＲはＨ、アルキル、アリールまたはアラルキルであり；Ｙ_１およびＹ_２は、同じでありまたは異なり、それぞれ独立してＯ、ＳまたはＮＲから選択され、このＲはＨ、アルキル、アリールまたはアラルキルであり；Ａ_１およびＡ_２は、同じでありまたは異なり、それぞれ独立してアルキレンであり；Ｚ_１およびＺ_２は、同じでありまたは異なり、それぞれ独立してＨ、（メタ）アクリロイル、グリシジル、または重合性官能基、例えばエポキシ（グリシジル以外）、エピスルフィド、（メタ）アクリレート（（メタ）アクリロイル以外）、（メタ）アクリルアミド、マレイミド、マレエート、フマレート、シンナメート、クロトネート、オキセタン、チオキセタン、アリル、スチレン類、オキサジン（例えばベンズオキサジン）、オキサゾリン、Ｎ−ビニルアミドおよびビニルエーテルなどを含む基のうちの１つもしくは複数から選択され；ｎ_１およびｎ_２は、同じでありまたは異なり、それぞれ独立して０または１である）に包含されてもよい。

Wherein X ₁ and X ₂ are the same or different and are each independently selected from CH ₂ , C═CH ₂ , C═O, C═S or C═NR, where R is H, alkyl Y ₁ and Y ₂ are the same or different and are each independently selected from O, S or NR, wherein R is H, alkyl, aryl or aralkyl; A ₁ and A ₂ are the same or different and are each independently alkylene; Z ₁ and Z ₂ are the same or different and are each independently H, (meth) acryloyl, glycidyl, or a polymerizable functional group such as Epoxy (other than glycidyl), episulfide, (meth) acrylate (other than (meth) acryloyl), (meth) acrylamide, maleimide, malee DOO, fumarate, cinnamate, crotonate, oxetane, Chiokisetan, allyl, styrene, oxazine (e.g., benzoxazine), oxazolines, are selected from one or more of the group, including N- vinyl amide and vinyl ethers; n ₁ and n ₂ may be the same or different and each independently 0 or 1).

  Compounds within structure I include dicarboxylic isomers of dicyclopentadienyl (“DCPD”) having the following structures IA-IF, where X is C═O and Y Is O, Z is H, and n is 0.

  Representative examples of compounds within structure I (wherein X is C═O, Y is O, Z is a group containing a polymerizable functional group, and n is 0) include the following: (Conveniently, compounds A to E are shown using a single structure, but other isomers similar to those shown in IA to IF may be used as well. Possible for compounds A to E).

  In yet another embodiment, the present invention provides for the chain through reaction of DCPD dicarboxylic acid and difunctional epoxy or polyfunctional epoxy resin in a controlled manner; or by reaction of dicarboxylic acid with DCPD diepoxide (Structure A). Compounds within the scope of extended structure I are provided.

  Representative examples of chain extended compounds of structure I (wherein X is C = O, Y is O and Z is a group containing a polymerizable functional group) include: Structures F to H are mentioned.

（式中、Ｒ_１およびＲ_２は、同じであってもまたは異なっていてもよく、それぞれ独立して二官能エポキシ樹脂または多官能エポキシ樹脂の骨格から選択され、ｎは１〜１０である）；

(Wherein R ₁ and R ₂ may be the same or different and are each independently selected from a skeleton of a bifunctional epoxy resin or a polyfunctional epoxy resin, and n is 1 to 10) ;

（式中、構造Ｇにおいて、Ｒ_３はジカルボン酸骨格であり；構造ＧおよびＨにおいて、ｎは１〜１０である）。これらの鎖延長された構造Ｆ〜Ｈは、構造の範囲内で、ＤＣＰＤ単位の頭−頭、頭−尾、または尾−頭配列を有し得る。

(In the structure G, R ₃ is a dicarboxylic acid skeleton; in structures G and H, n is 1-10). These chain-extended structures FH can have a head-to-head, head-to-tail, or tail-to-head arrangement of DCPD units within the structure.

Representative examples of compounds within the structure I (wherein X is CH ₂ , Y is O, A is CH ₂ , n is 1 and Z is H, (meth) acryloyl or glycidyl) Examples of the functional group) include the following structures J to L.
When Z is H,

Ｚが（メタクリロイル）である場合、

When Z is (methacryloyl)

Ｚがグリシジルである場合、

When Z is glycidyl,

  In yet another embodiment, a compound made from DCPD dicarboxylic acid and reacted to form a compound derivatized with different functional groups is provided.

Representative examples of compounds within structure II (wherein X ₁ and X ₂ are each C═O, Y ₁ and Y ₂ are each O, n ₁ and n ₂ are each 0, Z ₁ is a glycidyl, as the Z ₂ is (meth) acrylate), include the following structures M.

  Of course, DCPD derivatives within the scope of structures I and II may be used in conjunction with a curable resin component and a curing agent to form a thermosetting resin composition.

  For example, in another embodiment, the thermosetting resin composition comprises a curable resin component as well as a compound within the scope of structure I below:

（式中、ＸはＣＨ_２、Ｃ＝ＣＨ_２、Ｃ＝Ｏ、Ｃ＝ＳまたはＣ＝ＮＲであり、このＲはＨ、アルキル、アリールまたはアラルキルであり；ＹはＯ、ＳまたはＮＲであり、このＲはＨ、アルキル、アリールまたはアラルキルであり；Ａはアルキレンであり；ＺはＨ、（メタ）アクリロイル、グリシジル、または重合性官能基、例えばエポキシ（グリシジル以外）、エピスルフィド、（メタ）アクリレート（（メタ）アクリロイル以外）、（メタ）アクリルアミド、マレイミド、マレエート、フマレート、シンナメート、クロトネート、オキセタン、チオキセタン、アリル、スチレン類、オキサジン、オキサゾリン、Ｎ−ビニルアミドおよびビニルエーテルなどを含む基であり；ｎは０または１であり；ｍは２〜４である）；
ならびに／または
構造ＩＩの範囲内の化合物：

Wherein X is CH ₂ , C═CH ₂ , C═O, C═S or C═NR, where R is H, alkyl, aryl or aralkyl; Y is O, S or NR Where R is H, alkyl, aryl or aralkyl; A is alkylene; Z is H, (meth) acryloyl, glycidyl, or a polymerizable functional group such as epoxy (other than glycidyl), episulfide, (meth) acrylate (Other than (meth) acryloyl), (meth) acrylamide, maleimide, maleate, fumarate, cinnamate, crotonate, oxetane, thioxetane, allyl, styrenes, oxazine, oxazoline, N-vinylamide, vinyl ether and the like; n is 0 or 1; m is 2-4);
And / or compounds within structure II:

（式中、Ｘ_１およびＸ_２は、同じでありまたは異なり、それぞれ独立してＣＨ_２、Ｃ＝ＣＨ_２、Ｃ＝Ｏ、Ｃ＝ＳまたはＣ＝ＮＲから選択され、このＲはＨ、アルキル、アリールまたはアラルキルであり；Ｙ_１およびＹ_２は、同じでありまたは異なり、それぞれ独立してＯ、ＳまたはＮＲから選択され、このＲはＨ、アルキル、アリールまたはアラルキルであり；Ａ_１およびＡ_２は、同じでありまたは異なり、それぞれ独立してアルキレンであり；Ｚ_１およびＺ_２は、同じでありまたは異なり、それぞれ独立してＨ、（メタ）アクリロイル、グリシジル、または重合性官能基、例えばエポキシ（グリシジル以外）、エピスルフィド、（メタ）アクリレート（（メタ）アクリロイル以外）、（メタ）アクリルアミド、マレイミド、マレエート、フマレート、シンナメート、クロトネート、オキセタン、チオキセタン、アリル、スチレン類、オキサジン（例えばベンズオキサジン）、オキサゾリン、Ｎ−ビニルアミドおよびビニルエーテルなどを含む基のうちの１つもしくは複数から選択され；ｎ_１およびｎ_２は、同じでありまたは異なり、それぞれ独立して０または１である）を広く含む。

Wherein X ₁ and X ₂ are the same or different and are each independently selected from CH ₂ , C═CH ₂ , C═O, C═S or C═NR, where R is H, alkyl Y ₁ and Y ₂ are the same or different and are each independently selected from O, S or NR, wherein R is H, alkyl, aryl or aralkyl; A ₁ and A ₂ are the same or different and are each independently alkylene; Z ₁ and Z ₂ are the same or different and are each independently H, (meth) acryloyl, glycidyl, or a polymerizable functional group such as Epoxy (other than glycidyl), episulfide, (meth) acrylate (other than (meth) acryloyl), (meth) acrylamide, maleimide, malee DOO, fumarate, cinnamate, crotonate, oxetane, Chiokisetan, allyl, styrene, oxazine (e.g., benzoxazine), oxazolines, are selected from one or more of the group, including N- vinyl amide and vinyl ethers; n ₁ and n ₂ are the same or different and are each independently 0 or 1).

Compounds within the scope of structure I can be used as curing or fluxing agents, particularly when Z is hydrogen. When Z (and / or Z ₁ and / or Z ₂ ) is a group containing a polymerizable functional group, a compound within the structure I and / or II is useful as a co-reactant of the curable resin component. .

  In addition, the composition may include one or more of rubber toughening agents, adhesion promoters, wetting agents, colorants, antifoaming agents, and flow modifiers.

  The curable resin component may include a bisphenol-based epoxy resin such as bisphenol A, bisphenol F or bisphenol S epoxy resin, or a combination thereof. In addition, two or more different bisphenol epoxy resins within the same resin type (eg, A, F or S) may be used.

  Examples of commercially available bisphenol epoxy resins that are desirable for use herein include bisphenol F type epoxy resins (eg, Nippon Kayaku, Japanese RE-404-S, and Dainippon Ink & Chemicals, Inc.). EPICLON 830 (RE1801), 830S (RE1815), 830A (RE1826) and 830W, and Resolution RSL 1738 and YL-983U), and bisphenol A type epoxy resins (eg, Resolution YL-979 and 980).

  The above-mentioned bisphenol epoxy resin commercially available from Dainippon Ink & Chemicals, Inc. is a liquid undiluted epichlorohydrin-bisphenol F epoxy resin having a viscosity significantly lower than that of the conventional epoxy resin based on bisphenol A epoxy resin And has the same physical properties as liquid bisphenol A epoxy resin. The bisphenol F epoxy resin has a lower viscosity than the bisphenol A epoxy resin, and everything else is the same between the two epoxy resins, so the lower viscosity and thereby the faster flow underfill sealing material It becomes possible.

  The above bisphenol epoxy resins commercially available from Resolution are advertised as liquid epoxy resins with low chloride content. Bisphenol A epoxy resins have an EEW (g / eq) of between 180 and 195 and a viscosity at 25 ° C. of between 100 and 250 cps. The total chloride content of YL-979 is reported to be between 500-700 ppm, and the total chloride content of YL-980 is reported to be between 100-300 ppm. The total chloride content of RSL-1738 is reported to be between 500-700 ppm and the total chloride content of YL-983U is reported to be between 150-350 ppm.

  In addition to the bisphenol epoxy resin, other epoxy compounds are included in the curable resin component. For example, an alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carbonate may be used. Monofunctional, difunctional or polyfunctional reactive diluents may be used to adjust viscosity and / or reduce Tg, examples of which include butyl glycidyl ether, cresyl glycidyl ether, Examples include polyethylene glycol glycidyl ether or polypropylene glycol glycidyl ether.

  Epoxy resins suitable for use herein also include polyglycidyl derivatives of phenolic compounds, such as those commercially available from Resolution under the trade name EPON, for example, EPON 828, EPON 1001, EPON 1009, and EPON 1031. DER 331, DER 332, DER 334 and DER 542 as Dow Chemical Co .; Commercially available from Nippon Kayaku; and as BREN-S. Other suitable epoxy resins include polyepoxides prepared from polyols and the like, and polyglycidyl derivatives of phenol-formaldehyde novolacs, such as DEN 431, DEN 438 and DEN 439 from Dow Chemical. It is. Cresol analogs are also commercially available from Ciba Specialty Chemicals Corporation under the trade name ARALDITE, for example, ARALDITE ECN 1235, ARALDITE ECN 1273 and ARALDITE ECN 1299. SU-8 is a bisphenol A type epoxy novolac available from Resolution. Polyglycidyl adducts of amines, amino alcohols and polycarboxylic acids are also useful in this invention. I. C. Corporation's GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115; Ciba Specialty Chemicals' ARALDITE MY-720, ARALDITE 0500, and ARALDITE 0510, and Sherwin-Williams Co. PGA-X and PGA-C.

  Monofunctional epoxy co-reactive diluents suitable for use herein include those having a viscosity, typically less than about 250 cps, lower than the epoxy resin component.

The monofunctional epoxy co-reaction diluent should have an epoxy group with an alkyl group of about 6 to about 28 carbon atoms, examples of which include C _6-28 alkyl glycidyl ether, C _6-28 fatty acid glycidyl. _{Examples include} esters and _C6-28 alkylphenol glycidyl ethers.

  When such a monofunctional epoxy co-reactive diluent is included, the co-reactive diluent is in an amount up to about 5 weight percent to about 15 weight percent, for example about 8 weight percent, based on the total weight of the composition. Should be used in an amount from weight percent to about 12 weight percent.

  In addition to compounds and resins having epoxy functionality, of episulfides, oxetanes, thioxetanes, oxazines (eg benzoxazines), oxazolines, maleimides, itaconamides, nadimides, cyanate esters, (meth) acrylates, and combinations thereof Compounds and resins having one or more functional groups may be used.

  Compounds and resins having episulfide functionality may be those obtained by sulfurizing any of the epoxy resins. Oxetane may be one in which an epoxy resin is a four-membered oxygen-containing ring, and thioxetane may be one obtained by sulfurizing oxetane.

  Oxazines such as benzoxazine

（式中、ｏは１〜４であり、Ｘは、直接結合（ｏが２の場合）、アルキル（ｏが１の場合）、アルキレン（ｏが２〜４の場合）、カルボニル（ｏが２の場合）、チオール（ｏが１の場合）、チオエーテル（ｏが２の場合）、スルホキシド（ｏが２の場合）、もしくはスルホン（ｏが２の場合）から選択され、Ｒ_１はアリールである）、または、

(Wherein, o is 1 to 4, and X is a direct bond (when o is 2), alkyl (when o is 1), alkylene (when o is 2 to 4), carbonyl (o is 2) And thioether (when o is 1), thioether (when o is 2), sulfoxide (when o is 2), or sulfone (when o is 2), and R ₁ is aryl. ) Or

（式中、ｐは２であり、Ｙは、ビフェニル（ｐが２の場合）、ジフェニルメタン（ｐが２の場合）、ジフェニルイソプロパン（ｐが２の場合）、ジフェニルスルフィド（ｐが２の場合）、ジフェニルスルホキシド（ｐが２の場合）、ジフェニルスルホン（ｐが２の場合）、またはジフェニルケトン（ｐが２の場合）から選択され、Ｒ_４は水素、ハロゲン、アルキルまたはアルケニルから選択される）に包含され得る。

(Wherein p is 2 and Y is biphenyl (when p is 2), diphenylmethane (when p is 2), diphenylisopropane (when p is 2), diphenyl sulfide (when p is 2) ), Diphenyl sulfoxide (when p is 2), diphenyl sulfone (when p is 2), or diphenyl ketone (when p is 2), R ₄ is selected from hydrogen, halogen, alkyl or alkenyl ).

The cyanate ester may be selected from aryl compounds having at least one cyanate ester group in each molecule and is generally of the formula Ar (OCN) _m , where m is an integer from 2 to 5, It is an aromatic radical. The aromatic radical Ar contains at least 6 carbon atoms and can be derived from aromatic hydrocarbons such as, for example, benzene, biphenyl, naphthalene, anthracene, pyrene or the like. The aromatic radical Ar can also be derived from polynuclear aromatic hydrocarbons in which at least two aromatic rings are linked together by a bridging group. Aromatic radicals derived from novolak type phenol resins, that is, cyanate esters of these phenol resins are also included. The aromatic radical Ar may further comprise a non-reactive substituent bonded to the ring.

  Examples of such cyanate esters include, for example, 1,3-dicyanatobenzene; 1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1 , 6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene; 1,3,6-tricyanatonaphthalene; 4,4′-dicyanato-biphenyl; bis (4-cyanatophenyl) methane And 3,3 ′, 5,5′-tetramethylbis (4-cyanatophenyl) methane; 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane; 2,2-bis (3 , 5-dibromo-4-dicyanatophenyl) propane; bis (4-cyanatophenyl) ether; bis (4-cyanatophenyl) sulfide; 2,2-bis (4-cyanatophenyl) propane; − Anatophenyl) phosphite; tris (4-cyanatophenyl) phosphate; bis (3-chloro-4-cyanatophenyl) methane; cyanated novolak; 1,3-bis [4-cyanatophenyl-1- (methyl) Ethylidene)] benzene and cyanated bisphenol-terminated polycarbonate or other thermoplastic oligomers.

Compounds and resins having (meth) acrylate functionality may be selected from a number of materials, such as H ₂ C═CGCO ₂ R ¹ , where G is hydrogen, halogen, or 1 to about 4 R ¹ may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, or aryl groups having from 1 to about 16 carbon atoms , Any of these are optional, silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, sulfone and the like, optional May be substituted with or separated from each other.

  Additional (meth) acrylates suitable for use herein include polyfunctional (meth) acrylate monomers such as di- or tri-functional (meth) acrylates such as polyethylene glycol di (meth) acrylate, tetrahydrofuran ( (Meth) acrylate and di (meth) acrylate, hydroxypropyl (meth) acrylate ("HPMA"), hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate ("TMPTMA"), diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate ("TRIEGMA"), tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di- (pentamethylene glycol) dimethacrylate, tetra Tylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate and bisphenol A mono- and di (meth) acrylates such as ethoxylated bisphenol A (meth) Acrylates ("EBIPMA"), and bisphenol F mono and di (meth) acrylates such as ethoxylated bisphenol F (meth) acrylate.

  In addition, polyacrylates having (meth) acrylate functionality may be used. Particularly desirable are those prepared through controlled reduction polymerization techniques such as single electron transfer living radical polymerization techniques. See US Pat. No. 5,807,937 (Matyjaszwski), US Patent Application Publication No. 2010/0331493 (Percec), and US Patent Application Publication No. 2011/0060157 (Glaser).

  Still other (meth) acrylates that may be used herein are taught by silicone (meth) acrylate moieties (“SiMA”), eg, US Pat. No. 5,605,999 (Chu), This disclosure is hereby expressly incorporated herein by reference, including what is claimed.

  Of course, combinations of these (meth) acrylates may also be used.

  The curable resin component is present in the composition in an amount ranging from about 10 weight percent to about 95 weight percent, desirably from about 20 weight percent to about 80 weight percent, such as from about 40 weight percent to about 65 weight percent. Should.

  As a curing agent for epoxy resin, imidazole, dicyandiimide, carboxylic acid, anhydride, phenolic hardener, amine, thiol, alcohol and alkali may be used.

  Examples of imidazole include imidazole and derivatives thereof, such as isoimidazole, imidazole, alkyl-substituted imidazole, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, and butylimidazole. 2-heptadecenyl-4-methylimidazole, 2-methylimidazole, 2-undecenylimidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2-undecylimidazole, 2-heptadecylimidazole 2-phenylimidazole, 2-ethyl 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyano Tyr-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-guanaminoethyl-2-methylimidazole and addition products of imidazole methylimidazole and imidazole And n-heptadecyl-4-methylimidazole, and the like, wherein each alkyl substituent generally has a maximum of about 17 carbon atoms, preferably a maximum of about 6 Containing 1 carbon atom; aryl-substituted imidazoles such as phenylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1- (Dodeci Benzyl) -2-methylimidazole, 2- (2-hydroxyl-4-tert-butylphenyl) -4,5-diphenylimidazole, 2- (2-methoxyphenyl) -4,5-diphenylimidazole, 2- (3 -Hydroxyphenyl) -4-, 5-diphenylimidazole, 2- (p-dimethylaminophenyl) -4,5-diphenylimidazole, 2- (2-hydroxyphenyl) -4,5-diphenylimidazole, di (4 5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5-diphenylimidazole, 1-benzyl-2-methylimidazole, 2-p-methoxystyrylimidazole, and the like. In general, each aryl substituent has a maximum of about 10 carbon atoms, preferably Those containing up to about 8 carbon atoms.

  As a curing agent for free radical curing systems, peroxide is a suitable choice. For example, hydroperoxides such as cumene hydroperoxide ("CHP"), para-menthane hydroperoxide, t-butyl hydroperoxide ("TBH") and t-butyl perbenzoate may be used. Other useful peroxides include benzoyl peroxide, dibenzoyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, diacetyl peroxide, butyl 4,4-bis (t-butylperoxy) valerate, p-chlorobenzoyl Peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di- t-Butyl-peroxyhex-3-yne, 4-methyl-2,2-di-t-butylperoxypentane and combinations thereof.

  The curing agent should be present in an amount ranging from about 0.05 weight percent to about 10 weight percent of the total composition, desirably from about 0.1 weight percent to about 5 weight percent, for example about 1 weight percent.

  Inorganic filler components may be used, and inorganic filler components include reinforcing silica, such as fused silica, which may be untreated or treated to alter the surface chemistry. Also good. However, the inorganic filler component includes particles having an average particle size distribution in the range of 1 to 1,000 nanometers (“nm”). Commercially available examples of such filler particles are sold by Hans Chemie, Germany under the trade name NANOPOX, for example NANOPOX XP 22. NANOPOX filler is a monodispersed silica filler dispersion in epoxy resin up to about 50 weight percent. NANOPOX filler is usually considered to have a particle size of about 5 nm to about 80 nm. NANOPOX XP 22 is reported to contain 40 weight percent of silica particles having a particle size of about 15 nm in diglycidyl ether of bisphenol F epoxy resin.

  Hans Chemie also produces materials on the NANOPOX E transaction label. For example, Hans Chemie enables NANOPOX E brand products to fully impregnate electronic components that are otherwise difficult to seal, with a wide range of mechanical and thermal properties such as reduced shrinkage and thermal expansion, destruction It reports to provide toughness as well as elastic modulus. In Table A below, Hans Chemie provides information on the four NANOPOX E products listed.

Hans Chemie reports that the use of NANOPOX E brand products in epoxy formulations can significantly improve important properties. For example,
・ Low viscosity compared to conventional reinforcing fillers ・ No sedimentation ・ Increased fracture toughness, impact resistance and elastic modulus ・ Improved scratch resistance and wear resistance ・ Reduced shrinkage and thermal expansion ・ Many desired There is no improvement or at least no adverse effect on the properties of the material such as thermal stability, chemical resistance, glass transition temperature, weather resistance, dielectric properties

  The combination of NANOPOX E and conventional fillers, such as quartz, allows a reduction in the resin content in the formulation, which means that the total filler content can be increased to a level not previously achieved.

  Processability remains essentially unchanged compared to the respective base resin.

  NANOPOX E is used in applications where an improvement in the above properties is desired or necessary without compromising processability due to an excessive increase in viscosity (known for fumed silica). Examples of applications are encapsulating materials and coatings. It is important to emphasize the excellent impregnation properties of NANOPOX E, due to the small particle size and the absence of agglomerates. This also allows complete impregnation of electronic components that are otherwise difficult to seal.

According to the manufacturer, the NANOPOX E brand product is a colloidal silica sol in an epoxy resin matrix. The dispersed phase is composed of spherical SiO ₂ nanoparticles with a modified surface, which is less than 50 nm in diameter and has a very narrow particle size distribution. These spheres are only a few nanometers in size and are distributed without agglomerates in the resin matrix. This produces a very low viscosity dispersion with a SiO ₂ content of up to 40 weight percent. Nanoparticles are chemically synthesized from aqueous sodium silicate solutions.

  Other desirable materials for use as the inorganic filler component include those composed of or including aluminum oxide, silicon nitride, aluminum nitride, silica-coated aluminum nitride, boron nitride and combinations thereof. However, this naturally has the condition that the particles have an average particle size distribution in the range of 1 to 1,000 nm.

  The inorganic filler component should be used in an amount of about 10 to about 80 weight percent of the composition, such as about 12 to about 60 weight percent, desirably in an amount in the range of about 15 to about 35 weight percent. .

  In addition, adhesion promoters such as silane, glycidyltrimethoxysilane (commercially available from OSI as trade designation A-187) or gamma-aminopropyltriethoxysilane (commercially available from OSI as trade designation A-1100). ) May be used.

  Conventional additives may also be used in the compositions of the present invention to achieve certain desired physical properties for the composition, the cured reaction product, or both.

  The thermosetting resin composition can penetrate into the space between the circuit board and the semiconductor device, and functions as an underfill encapsulant in this manner. These compositions of the present invention also show a reduced viscosity, at least under high temperature conditions, so that they can penetrate into the space. A thermosetting resin composition can be prepared by selecting the types and proportions of various components so that the viscosity at 25 ° C. reaches 5,000 mPa · s or less, for example, 300 to 2,000 mPa · s. Desirably, this improves its permeability into the space between the circuit board and the semiconductor device (eg 10-500 μm).

  Referring to FIG. 1, there is shown an example of a subcomponent such as CSP, in which the thermosetting resin composition of the present invention is used.

  The semiconductor device 4 is formed by connecting the semiconductor chip 2 to the carrier substrate 1 and appropriately sealing the space between them with the resin 3. This semiconductor device is mounted at a predetermined position on the circuit board 5, and the electrodes 8 and 9 are electrically connected by appropriate connecting means such as solder. In order to improve the reliability, the space between the carrier substrate 1 and the circuit board 5 is sealed with a cured product 10 of a thermosetting resin composition. The cured product 10 of the thermosetting resin composition does not need to completely fill the space between the carrier substrate 1 and the circuit board 5, but even if the space is filled to the extent that the stress caused by the thermal cycle is relieved. Good.

The carrier substrate is a ceramic substrate made of Al ₂ O ₃ , SiN ₃ and mullite (Al ₂ O ₃ —SiO ₂ ); a substrate or tape made of a heat-resistant resin such as polyimide; glass reinforced epoxy, ABS, and phenolic substrate The circuit board may be generally used; as well as the like.

  With respect to the flip chip assembly, referring to FIG. 2, a flip chip assembly in which a semiconductor chip is mounted on a circuit board is shown, and the underfill is sealed with a thermosetting resin composition.

  The flip chip assembly 24 is formed by connecting the semiconductor chip 22 to the circuit board 21 and appropriately sealing the space between them with the thermosetting resin composition 23. This semiconductor device is mounted at a predetermined position on the circuit board 21 and the electrodes 25 and 26 are electrically connected by appropriate electrical connection means 27 and 28 such as solder. In order to improve reliability, the space between the semiconductor chip 22 and the circuit board 21 is sealed with the thermosetting resin composition 23 and then cured. The cured product of the thermosetting resin composition should completely fill this space.

  The means for electrically connecting the semiconductor chip to the carrier substrate is not particularly limited, and connection using high melting point solder or conductive (or anisotropic conductive) adhesive, wire bonding, and the like can be used. In order to facilitate connection, the electrodes may be formed as bumps. Furthermore, in order to improve the reliability and durability of the connection, the space between the semiconductor chip and the carrier substrate may be sealed with an appropriate resin. Examples of semiconductor devices that can be used in the present invention include CSP, BGA, and LGA.

  The circuit board may be composed of common materials such as glass reinforced epoxy, ABS, benzoxazine and phenolic resin.

  Next, in the mounting process, cream solder is printed at a required position on the circuit board, and dried appropriately to remove the solvent. Thereafter, the semiconductor device is mounted according to the pattern on the circuit board. By passing the circuit board through a reflow furnace and melting the solder, the semiconductor device is soldered. The electrical connection between the semiconductor device and the circuit board is not limited to the use of cream solder, but may be formed by using solder balls. Alternatively, this connection may be formed by a conductive adhesive or an anisotropic conductive adhesive. Furthermore, cream solder or the like may be applied or formed on either a circuit board or a semiconductor device. In order to facilitate subsequent repairs, the solder, conductive or anisotropic conductive adhesive used should be selected with its melting point, joint strength, and the like in mind.

  After the semiconductor device is electrically connected to the circuit board in this manner, the resulting structure should usually be subjected to a continuity test or the like. After passing such a test, the semiconductor device may be fixed thereto with a resin composition. In this method, in the case of failure, it is easier to remove the semiconductor device before fixing with the resin composition.

  Thereafter, the thermosetting resin composition may be applied around the semiconductor device. When this composition is applied to a semiconductor device, the composition penetrates into the space between the circuit board and the carrier substrate of the semiconductor device by capillary action.

  The thermosetting resin composition is cured by heating. At an early stage of this heating, the thermosetting resin composition exhibits a significant decrease in viscosity and thus an increase in fluidity, so that it penetrates more easily into the space between the circuit board and the semiconductor device. Furthermore, by providing an appropriate air hole in the circuit board, the thermosetting resin composition can completely penetrate the entire space between the circuit board and the semiconductor device.

  The amount of the thermosetting resin composition applied should be adjusted to almost completely fill the space between the circuit board and the semiconductor device.

  The thermosetting resin composition should normally be cured by heating at a temperature of about 100 ° C. to about 150 ° C. for about 5 to about 60 minutes, for example about 110 ° C. to about 130 ° C. for about 15 to about 45 minutes. . Accordingly, relatively low temperature and short time curing conditions may be used to achieve very good productivity. The subcomponents shown in FIG. 1 can be made in this way. Conventional epoxy-based compositions used for this purpose, such as those based solely on bisphenol A type epoxy resin or bisphenol F type epoxy resin as the epoxy resin, do not go through the same degradation pathway, but instead are about 300 It only starts to decay at ℃.

  After the semiconductor device is thus mounted on the circuit board, the resulting subcomponent may be tested for operability. If a defect is found, it can be repaired by the following method.

  The area near the defective semiconductor device is locally heated at a temperature of about 170 ° C. to about 240 ° C. for a time in the range of about 10 seconds to about 60 seconds, for example, a temperature of about 220 ° C. for about 30 seconds.

  As soon as the solder melts and the resin softens and the joint strength decreases, the semiconductor device is pulled apart.

  After the semiconductor device is removed, the residue of the curing reaction product of the thermosetting resin composition and the residue of the solder are left on the circuit board. The residue of the cured reaction product of the thermosetting resin composition can be removed, for example, by simply wiping the device with a cloth having low polishing power (see FIG. 3). Conventionally, the residue was softened by heating the residue to a predetermined temperature, swelling the residue with a solvent, or swelling the residue with a solvent while heating to a predetermined temperature, and then processed. It was necessary to scrape the reaction product (see FIG. 3).

  Finally, a new semiconductor device may be mounted again on the cleaned circuit board by the same method as described above. In this way, repair of the defective part is completed.

  If a defect is found on the circuit board, the residue of the curing reaction product of the thermosetting resin composition left on the bottom of the semiconductor device and the residue of the solder are removed by the same method as described above. Thus, the semiconductor device can be reused.

  Although the composition of the present invention has been described as being primarily useful as an underfill encapsulant, the composition of the present invention can be used as a structural adhesive in liquid compression molding applications, for example, as mobile phones such as smartphones and tablets. It may also be used in the production of electronic display devices, semiconductor packaging films, short / long term encapsulants for passive electronic components, and coatings.

  The invention is further illustrated by the following non-limiting examples.

Composition

Example 1

  In a 1 L four-necked flask equipped with a mechanical stirrer and dropping funnel, DCPD dicarboxylic acid (“DCPD diacid”) (50 g, 227 mmol) was placed with DMSO (300 mL). KOH (26.8 g) dissolved in 30 mL water was added slowly over 5 minutes and stirred continuously for another 15 minutes. The reaction mixture was then heated at a temperature of 50 ° C. using an oil bath. Epibromohydrin (124.4 g, 908 mmol) in 25 mL DMSO was added dropwise over 2 hours and stirred continuously for an additional 6 hours.

The reaction mixture was extracted with 600 mL of ethyl acetate, washed with aqueous NaHCO ₃ solution, washed several times with water, and then dried over anhydrous MgSO ₄ . The solvent was evaporated to give a brown liquid, which was diluted with 50 mL of toluene and distilled to give the diglycidyl ester of DCPD diacid (“DCPD epoxy”) (60 g, 80% yield). It was.

Example 2

A 1 L four-necked flask equipped with a nitrogen inlet and a mechanical stirrer was charged with DCPD diacid (15.2 g, 69 mmol) and resorcinol diglycidyl ether (30.7 g, 138 mmol) in THF (450 mL). . After stirring for 30 minutes, a catalytic amount of tetrabutylammonium iodide (1.27 g, 3.44 mmol) was added and the mixture was heated to reflux for 36 hours. When infrared (“IR”) spectroscopy was performed, the results indicated the presence of a carbonyl band at 1707 cm ^−1, which differs in nature from DCPD diacid.

After the reaction mixture was cooled to room temperature, the THF was evaporated and 600 mL of ethyl acetate was added to the residue. The organic layer was washed several times with water, washed with saturated aqueous NaHCO ₃ and then washed again with water. After drying over anhydrous MgSO ₄ , the solvent was evaporated to give the above DCPD chain-extended epoxy as a dark brown viscous liquid (35 g, 78% yield).

IR spectroscopic analysis of DCPD chain extended epoxy showed a carbonyl band at 1707 cm ⁻¹ .

Example 3

DCPD epoxy (2.06 g, 6.2 mmol), methacrylic acid (0.54 g, 6.2 mmol), tetrabutylammonium iodide (100 mg) and t-butylcatechol (30 mg) together with THF (20 mL) in a round bottom flask The mixture was refluxed for 5 hours and mixed. After the reaction mixture was cooled to room temperature, ethyl acetate was added and the organic layer was washed twice with saturated aqueous NaHCO ₃ , washed with aqueous K ₂ CO ₃ , and dried over anhydrous MgSO ₄ . The solvent was then evaporated to give DCPD hybrid epoxy-methacrylate as a dark brown viscous liquid (1.82 g, 70% yield).

Example 4

In a 500 mL four-necked flask equipped with a nitrogen inlet, DCPD diacid (35.7 g, 162 mmol) was placed in THF (300 mL). The mixture was cooled in an ice-salt bath and oxalyl chloride (61.7 g, 486 mmol) was added dropwise over 5 minutes. The reaction mixture was allowed to reach room temperature and stirred for an additional 4 hours. The solvent and excess oxalyl chloride were evaporated, the residue was dissolved in THF (200 mL) under a nitrogen atmosphere and the solution was cooled with ice. Triethylamine (41 g, 405 mmol) was added with stirring, then HEMA (42.2 g, 324 mmol) was added over 30 minutes, and t-butylcatechol (140 mg) was added with stirring. After about 4 hours, THF was evaporated and the reaction mixture was extracted with ethyl acetate (400 mL), washed four times with water and dried over anhydrous MgSO ₄ . The solvent was evaporated to give DCPD dimethacrylate as a dark brown liquid (57 g, 73% yield), which was purified by column chromatography.

Example 5

DCPD diacid (29 g, 132 mmol) was dissolved in DMF, K ₂ CO ₃ (36 g, 263 mmol) was added and stirred for 30 minutes. Thereafter, allyl bromide (42 g, 347 mmol) was added in portions over 10 minutes. The reaction mixture was stirred at room temperature overnight. The reaction mixture was then extracted with ethyl acetate (500 mL), washed 4 times with water and dried over anhydrous MgSO ₄ . The solvent was evaporated to give the diallyl ester of DCPD diacid (31 g, 78% yield).

Example 6

In a 250 mL flask equipped with a magnetic stir bar, DCPD diacid (4.5 g, 20.4 mmol), DMSO (100 mL), and K ₂ CO ₃ (3.39 g, 24.5 mmol) were added and stirred for 15 minutes. 4-Vinylbenzyl chloride (7.2 g, 47.2 mmol) was added and the reaction mixture was stirred at room temperature overnight.

IR spectroscopic analysis showed a carbonyl band at 1709 cm ⁻¹ as the ester.

The reaction mixture was extracted with ethyl acetate, washed several times with water and dried over anhydrous MgSO ₄ . The solvent was evaporated and the reaction mixture was purified by column chromatography to give the distyrene derivative of DCPD diacid as a yellow oil (5.3 g, 58% yield).

Example 7

A 250 mL three-necked flask equipped with a nitrogen inlet and a magnetic stir bar was charged with 2 M cyclopentadienide sodium THF solution (30 ml, 60 mmol) in THF (50 mL). The suspension was cooled with ice for about 30 minutes, and then a solution of (2-bromoethoxy) -tert-butyldimethylsilane (14.34 g, 60 mmol) was added dropwise over about 30 minutes. The mixture was stirred at the same temperature for about 2 hours and then at room temperature overnight. The THF was evaporated and the product was extracted with ethyl acetate (200 mL), washed with water and dried over anhydrous MgSO ₄ . The solvent was evaporated to obtain an intermediate crude silyl derivative of 2-hydroxyethylcyclopentadiene, which was then dimerized by heating at a temperature of about 110 ° C. for about 1.5 hours to produce an intermediate DCPD diethanol silyl derivative. Got.

To a solution of this crude product in THF (50 mL) was added 1M TBAF in THF (60 mL, 60 mmol) and the mixture was stirred at room temperature overnight. The THF was evaporated and the product was extracted with ethyl acetate (200 mL), washed with water and dried over anhydrous MgSO ₄ . Evaporation of the solvent gave DCPD diethanol as a brown oil (8.1 g, 61% yield).

Example 8

Bishydroxyethyl DCPD (1.05 g, 4.8 mmol) was placed in a 100 mL three-necked flask equipped with a nitrogen inlet and a magnetic stir bar in CH ₂ Cl ₂ (25 mL). Triethylamine (2.41 g, 23.8 mmol) and a catalytic amount of DMAP (50 mg) were added. The resulting mixture was cooled with ice and methacrylic anhydride (2.94 g, 19.1 mmol) was added dropwise. Stir at the same temperature for about 30 minutes, then at room temperature for an additional 3 hours, and then add aqueous NaHCO ₃ (30 mL). The CH ₂ Cl ₂ was then evaporated and the product was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous MgSO ₄ . t-Butylcatechol (200 ppm) was added and the solvent was evaporated to give the dimethacrylate ester of DCPD diethanol (1.4 g, 82% yield).

Example 9

To a 100 mL three-necked flask equipped with a nitrogen inlet and a magnetic stir bar, NaH (2.18 g, 60% dispersion in oil, 54.4 mmol) was added in dry DMF (25 mL). The solution was cooled in an ice bath and a solution of bishydroxyethyl DCPD (3 g, 13.6 mmol) in dry DMF (25 mL) was added slowly over about 15 minutes. After further stirring for about 30 minutes, epibromohydrin (7.47 g, 54.4 mmol) was slowly added dropwise. After the mixture was warmed to room temperature and stirred overnight, isopropanol was added followed by toluene (200 ml). The organic layer was washed several times with water and dried over anhydrous MgSO ₄ before the solvent was evaporated. The crude product of the reaction was purified by column chromatography to isolate diglycidyl ether (2.3 g, 51% yield).

Thermosetting Resin Composition Thermosetting resin compositions may be prepared from the components listed in Table 1 below, each sample containing less than 1 weight percent defoamer, and silane adhesion promoter. Including.

  HYSOL UF 3808 and HYSOL UF 3800 commercially available from Henkel Electronic Materials, LLC, Irvine, California are used for comparison purposes and are simply referred to by product name.

Physical Properties In an uncured state, each sample is dispensed from a syringe or jet dispenser alongside a 6 × 6 mm wafer level CSP (“WL-CSP”: wafer-level CSP) at a dispensing temperature of about 25 ° C. Noted. The sample flowed into the underfill space between the WL-CSP and the circuit board to which the sample was attached in less than 30 seconds by capillary action.

  Samples were cured by exposure to high temperature conditions ranging from about 100 ° C. to about 150 ° C. for about 10 to about 60 minutes.

  Referring to Tables 5 through 7 below, dynamic mechanical analysis ("DMA") data for the cured compositions, Samples A through K are shown.

  FIG. 4 shows the elastic modulus with respect to temperature for each of the samples shown in Table 5.

  FIG. 5 shows the elastic modulus with respect to temperature for each of the samples shown in Table 6.

  FIG. 10 shows the tan delta versus temperature for each of the samples shown in Table 7.

Thermal Cycle Test Referring to Table 8 below, the elastic modulus values from the thermal cycle results of dynamic mechanical analysis are listed, which are -85 ° C to 250 ° C at a ramp rate of 3 ° C / min. The cycle to -85 [deg.] C. is then made 4 cycles.

  Referring to FIGS. 6-8, the samples shown in Table 8 are shown, and FIG. 9 shows the elastic modulus versus temperature trace for HYSOL UF 3808.

  For the sample, Δtanδ, which is the difference in tanδ peak (glass transition temperature or Tg) between cycle 1 and cycle 4, was calculated. The difference in modulus at 25 ° C. between cycle 1 and cycle 4 was also calculated for the sample. For samples K, L and M, a decrease in the respective Tg was observed; the opposite result was observed for HYSOL UF 3800 and HYSOL UF 3808. The observed decrease in modulus was more pronounced for samples K, L, and M than HYSOL UF 3800 and HYSOL UF 3808.

  Referring to Table 9 below, additional thermal cycling evaluations are shown for the two samples compared to the commercial products HYSOL UF 3800 and HYSOL UF 3808. One thermal cycle condition (thermal cycle 1) is performed at a temperature of −40 ° C. to 85 ° C. in 30 minutes per cycle; another thermal cycle (thermal cycle 2) is performed at a temperature of −55 ° C. to 125 ° C. Performed at 30 minutes per cycle. The component used was a 6 × 6 mm WL-CSP.

Repair Using a hot air generator, an area near the WL-CSP fixed to the circuit board with a sample was heated by applying hot air at a temperature of 285 ° C. for 30 seconds. Thereafter, the WL-CSP was removed by vacuum adsorption, and the WL-CSP was lifted with an appropriate nozzle. All remaining residue of the cured reaction product was removed from the substrate by wiping the surface. Referring to FIG. 3, a process flow diagram is shown.

Claims (12)

A curable composition wherein the reaction product of the curable composition is degradable in a controlled manner upon exposure to higher temperature conditions than the temperature conditions used to cure the composition,
(A) a curable resin component;
(B) a curing agent;
(C) a diene / dienophile pair functionalized with at least two carboxylic acid groups, wherein the diene / dienophile pair is a compound of formula I:

(Wherein X is C = O; Y is O; A is alkylene; Z is H; n is 0 or 1; m is 2-4)
A curable composition.   A semiconductor device and a circuit board to which the semiconductor device is electrically connected, or an electronic device including a semiconductor chip and a circuit board to which the semiconductor chip is electrically connected, each of the semiconductor device and the circuit board The curable composition of claim 1 is assembled as an underfill encapsulant between or between the semiconductor chip and the circuit board, and the reaction product of the composition cures the composition. An electronic device that is capable of softening and losing adhesion under exposure to temperature conditions that exceed the temperature conditions used to cause. Between a semiconductor device including a semiconductor chip mounted on a carrier substrate and a circuit board to which the semiconductor device is electrically connected, or between a semiconductor chip and a circuit board to which the semiconductor chip is electrically connected A method for sealing an underfill, wherein the steps of the method include:
(A) dispensing the composition of claim 1 into an underfill between the semiconductor device and the circuit board or between the semiconductor chip and the circuit board;
(B) exposing the dispensed composition to a temperature in the range of 100 ° C. to 150 ° C. for about 10 minutes to about 1 hour to cause the composition to form a reaction product. . A curable composition wherein the reaction product of the curable composition is degradable in a controlled manner upon exposure to higher temperature conditions than the temperature conditions used to cure the composition,
(A) a curable resin component;
(B) a curing agent;
(C) a diene / dienophile pair functionalized with at least two groups reactive with the curable resin component, wherein the diene / dienophile pair is a compound of formula II:

Wherein X ₁ and X ₂ are C═O, Y ₁ and Y ₂ are each O, A ₁ and A ₂ are each alkylene; Z ₁ and Z ₂ are the same or different Each independently selected from H, (meth) acryloyl, glycidyl, epoxy or (meth) acrylate; n ₁ and n ₂ are 0)
A curable composition.   The curable resin component is a member selected from the group consisting of epoxy, episulfide, oxetane, thioxetane, oxazine, maleimide, itaconamide, nadimide, (meth) acrylate, (meth) acrylamide, and combinations thereof. Item 5. The composition according to Item 1 or 4.   5. A composition according to claim 4, wherein the two reactive groups are the same.   The composition of claim 1, wherein the two carboxylic acid groups are the same.   5. The composition of claim 4, wherein the two reactive groups are different.   The composition according to claim 1 or 4, wherein the curing agent is selected from imidazole, dicyandiimide, carboxylic acid, anhydride, phenolic hardener, amine, thiol, alcohol, and alkali.   5. A composition according to claim 1 or 4, wherein the diene of the diene / dienophile pair is cyclopentadiene.   The composition of claim 1, wherein the high temperature condition is about 170 ° C. or higher.   The composition of claim 1, wherein the curing temperature condition is from about 100C to about 150C.

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